CN102998381A - Method for measuring content of phthalic acid ester in tipping paper for cigarettes - Google Patents
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Abstract
The invention discloses a method for measuring content of phthalic acid ester in tipping paper for cigarettes. The method comprises the following steps of: preparing an internal standard solution, preparing a standard solution, preparing a mixed standard working solution, and performing gas chromatograph-mass spectrometer (GC/MS) analysis and detection. By utilizing the GC/MS, the content of 18 phthalic acid esters in tipping paper for cigarette can be measured, and the method has the advantages of high rapidness and accuracy.
Description
Technical field
The present invention relates to the physical and chemical inspection technical field of adjuvant in the cigarette tipping paper, be specifically related to the assay method of phthalic acid ester content in a kind of cigarette tipping paper.
Background technology
Phthalic ester (PAEs) refers to the esterification derivative of phthalic acid, generally refers to the ester of the alcohol formation of phthalic acid and 4～15 carbon.PAEs can well increase plasticity and the flowability when shaping, and can increase the pliability of product, can increase the tack of coating, printing ink, so as plastifier and softening agent, PAEs is widely used in the products such as plastic cement, rubber, leather, adhesive, coating, printing ink.A large amount of ink printing materials that use add the processing characteristics that the PAEs compounds can improve printing ink, so PAEs may exist in cigarette packaging material in the printing ink in the production of cigarettes process.
PAEs can enter human body by approach such as drinking-water, feed, skin contact and breathings, detects phthalic ester in people's the body fluid such as urine, milk, blood and seminal fluid.Phthalic ester is that hormone is disturbed in the endocrine of in the world key monitoring, can disturb particularly reproductive function of human endocrine, and it damages and can cause cell mutation, final teratogenesis and carcinogenic when serious.In addition, studies show that this material is also influential to children's neurodevelopment.
At present to the mensuration of phthalate material mainly in fields such as atmosphere, water, cosmetics, textile, soil, toy and articles for children, food plastic wrappage and medical supplies.Usually adopt Soxhlet to extract or the method such as ultrasonic extraction to solid kind determination technology, because Soxhlet extraction time is long, the quantity of solvent of use is large, complex operation, the therefore common method of the ultrasonic extraction of employing; Detection method generally adopts the GC-MS method.
(isopropyl alcohol extraction-vapor-phase chromatography is measured phthalate compound in cigarette tipping paper and the wrapping paper to Liu Zechun etc. simultaneously, analytical instrument, 2010,2:30-35) take by weighing the 0.25g sample, take anethole as interior mark, adopt the isopropyl alcohol ultrasonic extraction, vapor-phase chromatography (GC-FID) is measured the method for 14 kinds of phthalate compounds in cigarette tipping paper and the wrapping paper, the shortcoming that the method exists is not to pre-service such as sample shred, and be simple filtration and do not take other control techniques to extract, cause sample solution dirtier, larger to the instrument infringement.
Chinese invention patent CN102331475A discloses a kind of method of measuring phthalate compound content in the cigarette tipping paper, the method with cigarette tipping paper to contain the ultrasonic extraction of interior target absolute ethyl alcohol, after crossing organic filter membrane, GC/MS analyzes 7 kinds of phthalate compounds, this method is easy and simple to handle, but the filtrate color of sample segment is dark, impurity is more, may have certain interference to the mensuration of target compound, and the GC/MS system is also had infringement.
Chinese invention patent CN102507823A discloses the assay method that a kind of cigarette is used phthalic acid ester content in the paper material, this assay method is with the water infiltration sample, make the composite print wrapping paper realize separating of layer and layer, improved the organic extraction solvent isopropyl alcohol that adds subsequently to the effect of extracting of phthalic ester in the water base adhesive between layers.This method is applied widely, is particularly useful for such as internal lining paper and this class composite print paper product of cigarette packs skin wrapping paper, but with the water infiltration product, can increases time for sample pretreatment.
Summary of the invention
The object of the present invention is to provide the assay method of phthalic acid ester content in a kind of cigarette tipping paper.
In order to realize above purpose, the technical solution adopted in the present invention is: the assay method of phthalic acid ester content in a kind of cigarette tipping paper, adopt internal standard method, and may further comprise the steps:
(1) preparation inner mark solution
Take by weighing the internal standard compound Ergol, being mixed with concentration is the Ergol ethanolic solution of 20mg/mL;
(2) preparation sample solution
Cut the cigarette tipping paper sample, carry out according to the regulation of YC171-2008, namely accurately cut the tipping paper sample (should comprise monolateral) of long 200mm, wide 40mm; Afterwards the cigarette that cuts is cut into the fragment that is not more than 0.5cm * 0.5cm with the paper material sample, described fragment is placed 50mL tool plug triangular flask, in described 50mL tool plug triangular flask, accurately add 20mL ethanol, and the inner mark solution of 50 μ L; Afterwards ultrasonic extraction 30 minutes, after being cooled to room temperature, get the 1mL extract and put into 25mL tool plug triangular flask, the normal hexane that adds 1mL water and 5mL in the described 25mL tool plug triangular flask, described 25mL tool plug triangular flask is placed on the oscillator, with the speed oscillation of 200rpm 10 minutes, leave standstill, get supernatant liquor as sample solution, to be measured;
(3) preparation hybrid standard working solution
Take by weighing 18 kinds of phthalic ester standard items, be mixed with the hybrid standard working solution with seven grades of concentration gradients;
(4) GC-MS analyzing and testing
Adopt GC-MS respectively described hybrid standard working solution and sample solution to be carried out analyzing and testing, then carry out the quantitative test of phthalic ester with internal standard method, namely the selection quasi-molecular ions Area Ratio with phthalic ester and interior mark Ergol carries out regretional analysis to its respective concentration, obtains typical curve; Sample solution is measured, record the selection quasi-molecular ions Area Ratio of phthalic ester and interior mark Ergol, the substitution typical curve, get the repefral (DMP) in the smoke paper using material sample, diethyl phthalate (DEP), diallyl phthalate (DAP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), phthalic acid two (2-methoxyl) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate, di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), the content of totally 18 kinds of phthalic esters.
Further, the compound method of hybrid standard working solution is described in the step (3): take by weighing respectively 0.1g phthalic ester standard items, place same 10mL volumetric flask, with ethanol dissolving and constant volume, being mixed with each phthalic ester concentration is the hybrid standard storing solution I of 10mg/mL; Then accurately pipette the described hybrid standard storing solution of 1mL I, place another 10mL volumetric flask, then use the ethanol constant volume, being mixed with each phthalic ester concentration is the hybrid standard storing solution II of 1mg/mL; Accurately pipette the hybrid standard storing solution II of 0.05mL, 0.1mL, 0.2mL, 0.5mL, accurately pipette the hybrid standard storing solution I of 0.1mL, 0.2mL, 0.5mL, place respectively the tool plug triangular flask of 7 50mL, then in the tool plug triangular flask of described 7 50mL, accurately add respectively 20mL ethanol, inner mark solution with 50 μ L shakes up; Get the 1mL mentioned solution and put into 25mL tool plug triangular flask, the normal hexane that adds 1mL water and 5mL in the described 25mL tool plug triangular flask, then place on the oscillator with the speed oscillation of 200rpm 10 minutes, leave standstill, get supernatant liquor as the hybrid standard working solution, the concentration of the hybrid standard working solution of preparation is: 0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL, 50 μ g/mL.
Described phthalic ester standard items are: repefral (DMP), diethyl phthalate (DEP), diallyl phthalate (DAP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), phthalic acid two (2-methoxyl) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate, di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), totally 18 kinds of phthalic esters.
The GC condition that adopts when GC-MS detects is: chromatographic column: HP-5ms Fused-silica capillary column, column length 30m, internal diameter 0.25mm, thickness 0.25 μ m; Injector temperature: 280 ℃, sample size: 1 μ L, use shunt mode, split ratio is 10:1; Temperature programme: 60 ℃ of initial temperatures, kept 1 minute, the heating rate with 20 ℃/min rises to 220 ℃ again, and then the heating rate with 10 ℃/min rises to 280 ℃, keeps 15 minutes; Carrier gas is helium, constant speed 1.0mL/min; The mass spectrum condition that adopts is: ionization mode: electron bombardment ionization source, ionizing energy: 70eV; Transmission line temperature: 280 ℃; Ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Mensuration mode: select the scanning of ion surveillance style; Solvent delay: 6 minutes.
The assay method of phthalic acid ester content is optimized the disposal route of sample and the testing conditions of GC-MS instrument in the cigarette tipping paper provided by the invention, and compared with prior art, assay method provided by the invention has following technique effect:
(1) the present invention takes ethanol ultrasonic extraction method, to not belonging to the cigarette tipping paper of composite print category, under the prerequisite that guarantees extraction efficiency, compares isopropyl alcohol and has reduced toxicity and environmental pollution to the testing staff, has reduced simultaneously testing cost.
(2) assay method of the present invention is compared patent CN102331475A, taking has increased the step that adds entry and normal hexane in the sample extraction liquid after the ethanol ultrasonic extraction, the normal hexane layer clarification that obtains, colourless, aqueous layer is muddy or certain color is arranged, thereby has realized the purification and impurity removal effect to extract; This is because ethanol can extract the pigment in the printing ink that is attached on the tipping paper get off, therefore extract has color, the extract of some sample is muddy state, existing method is taked organic membrane filtration removal of impurities, although filtrate clarification, but color is arranged, these pigment have certain damage effect to the GC-MS system, and in the process with organic membrane filtration, phthalic ester in syringe or the filter membrane material may be introduced in the sample solution, measurement result is produced interference, affect the accuracy of measurement result.Assay method of the present invention is compared patent CN102507823A, although all adopted the purification method of liquid-liquid extraction, has reduced the process with the water infiltration sample, so simplified sample pretreatment process, has shortened time for sample pretreatment.
(3) can to measure the kind of phthalic ester many for assay method provided by the invention, according to Ministry of Health of the People's Republic of China " about announce in the food may illegal interpolation non-edible material from soybeans and the easy bulletin of the food additives list (the 6th batch) of abuse (Ministry of Public Health's bulletin 2011 No. 16). (2011-06-01) " in 17 kinds of phthalic esters listing, and the diallyl phthalate paid close attention to of tobacco business, assay method when the inventive method has been investigated 18 kinds of phthalic esters altogether, the repefral (DMP) that these 18 kinds of phthalic esters relate to except patent CN102331475A and CN102507823A, diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), phthalic acid two (2-ethyl) own ester (DEHP), 7 kinds of phthalic esters of di-n-octyl phthalate (DNOP) have also increased diallyl phthalate (DAP), phthalic acid two (2-methoxyl) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), diphenyl phthalate, dinonyl phthalate (DNP), 11 kinds of phthalic esters of diisononyl phthalate (DINP).
(4) assay method provided by the invention have operation accurately, the extract degree of purification is good, highly sensitive and the advantage of good reproducibility, calculate detectability (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), diisononyl phthalate is 7.8mg/kg and dinonyl phthalate 18.0mg/kg, and the detectability of other 16 kinds of phthalic esters is between 0.3mg/kg～4.7mg/kg; Recovery of standard addition is 94.9%～109.0%, and average relative standard deviation (RSD) is 1.3%～6.8%.
1. the detectability of assay method of the present invention
Repefral (DMP) with variable concentrations, diethyl phthalate (DEP), diallyl phthalate (DAP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), phthalic acid two (2-methoxyl) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate, di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), totally 18 kinds of phthalic ester hybrid standard working solutions inject GC-MS, calculate detectability (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), diisononyl phthalate is 7.8mg/kg and dinonyl phthalate 18.0mg/kg, and the detectability of other 16 kinds of phthalic esters is between 0.3mg/kg～4.7mg/kg.Concrete detectability data are shown in Table 1;
2. the repeatability of assay method of the present invention and recovery of standard addition
In the cigarette tipping paper sample, add repefral (DMP), diethyl phthalate (DEP), diallyl phthalate (DAP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), phthalic acid two (2-methoxyl) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate, di-n-octyl phthalate (DEHP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), totally 18 kinds of phthalic ester hybrid standard working solutions, then the preparation and the GC-MS that carry out respectively sample solution analyze, and calculate its recovery according to adding the scalar sum measured value, the results are shown in Table shown in 1, as can be seen from Table 1, recovery of standard addition is 94.9%～109.0%, and average relative standard deviation (RSD) is 2.6%～7.2%; The recovery that assay method of the present invention is described is high, good reproducibility.
Detectability, recovery of standard addition and the repeatability (n=6) of table 118 kind of phthalic ester
Description of drawings
Fig. 1 be hybrid standard working solution in the embodiment of the invention 1 chromatogram (1-DMP wherein, 2-DEP, 3-DAP,
4-DIBP, 5-DBP, 6-DMEP, 7-BMPP, 8-DEEP, 9-DPP, 10-DHXP, 11-BBP, 12-DBEP, 13-DCHP, 14-DEHP, 15-diphenyl phthalate, 16-DNOP, 17-DINP, mark in the 18-DNP, IS-);
Fig. 2 is the chromatogram (wherein 5-DBP marks in the IS) of sample solution in the embodiment of the invention 1.Embodiment
Below by specific embodiment technical scheme of the present invention is elaborated.
Embodiment 1
The assay method of phthalic acid ester content in certain blue cigarette tipping paper adopts internal standard method, may further comprise the steps:
(1) preparation inner mark solution
Take by weighing the internal standard compound Ergol, be mixed with the Ergol ethanolic solution, the concentration of Ergol is 20mg/mL in the Ergol ethanolic solution, and this Ergol ethanolic solution is inner mark solution.
(2) preparation sample solution
Regulation according to YC171-2008 cuts certain cigarette tipping paper, namely accurately cut long 200mm, certain cigarette tipping paper sample of wide 40mm (should comprise one monolateral), quality is about 0.3g, the cigarette tipping paper that cuts placed on the balance weigh, the cigarette tipping paper that will cut afterwards is cut into the fragment that is not more than 0.5cm * 0.5cm, fragment is placed 50mL tool plug triangular flask, in this 50mL tool plug triangular flask, accurately add 20mL ethanol and 50 μ L inner mark solutions, afterwards ultrasonic extraction 30 minutes, after being cooled to room temperature, get the 1mL extract and put into 25mL tool plug triangular flask, add the water of 1mL and the normal hexane of 5mL in this 25mL tool plug triangular flask, this 25mL tool plug triangular flask is placed on the oscillator with the speed oscillation of 200rpm 10 minutes, leave standstill, get supernatant liquor as sample solution, to be measured.
(3) preparation hybrid standard working solution
Take by weighing respectively 0.1g phthalic ester standard items, place same 10mL volumetric flask, with ethanol dissolving and constant volume, being mixed with each phthalic ester concentration is the hybrid standard storing solution I of 10mg/mL; Then accurately pipette the described hybrid standard storing solution of 1mL I, place another 10mL volumetric flask, then use the ethanol constant volume, being mixed with each phthalic ester concentration is the hybrid standard storing solution II of 1mg/mL; Accurately pipette the hybrid standard storing solution II of 0.05mL, 0.1mL, 0.2mL, 0.5mL, accurately pipette the hybrid standard storing solution I of 0.1mL, 0.2mL, 0.5mL, place respectively the tool plug triangular flask of 7 50mL, then in the tool plug triangular flask of described 7 50mL, accurately add respectively 20mL ethanol, inner mark solution with 50 μ L shakes up; Get the 1mL mentioned solution and put into 25mL tool plug triangular flask, the normal hexane that adds 1mL water and 5mL in the described 25mL tool plug triangular flask, then place on the oscillator with the speed oscillation of 200rpm 10 minutes, leave standstill, get supernatant liquor as the hybrid standard working solution, the concentration of the hybrid standard working solution of preparation is: 0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL, 50 μ g/mL.
(4) GC-MS analyzing and testing
The hybrid standard working solution for preparing is injected GC-MS, carry out the quantitative test of phthalic ester with internal standard method, namely the selection quasi-molecular ions Area Ratio with phthalic ester and internal standard compound Ergol carries out regretional analysis to its respective concentration, obtain typical curve, wherein, the chromatogram of hybrid standard working solution as shown in Figure 1, the chromatogram of sample solution is as shown in Figure 2; Equation of linear regression, the related coefficient corresponding with typical curve of each phthalic ester are shown in Table 2.
The equation of linear regression of each phthalic ester of table 2, related coefficient
Sample solution is measured, measured the selection quasi-molecular ions Area Ratio of phthalic ester and internal standard compound Ergol, the substitution typical curve draws that n-butyl phthalate is 49.3mg/kg in certain cigarette tipping paper, does not detect other phthalic ester; The GC condition that adopts when wherein, GC-MS detects is: chromatographic column: HP-5ms Fused-silica capillary column, column length 30m, internal diameter 0.25mm, thickness 0.25 μ m; Injector temperature: 280 ℃, sample size: 1 μ L, use shunt mode, split ratio is 10:1; Temperature programme: 60 ℃ of initial temperatures, kept 1 minute, the heating rate with 20 ℃/min rises to 220 ℃ again, and then the heating rate with 10 ℃/min rises to 280 ℃, keeps 15 minutes; Carrier gas is helium, constant speed 1.0mL/min; The mass spectrum condition that adopts is: ionization mode: electron bombardment ionization source, ionizing energy: 70eV; Transmission line temperature: 280 ℃; Ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Mensuration mode: select the scanning of ion surveillance style; Solvent delay: 6 minutes.
18 kinds of phthalic esters and the quantitative and qualitative selection ion of internal standard compound Ergol BB see Table 3.
Table 318 kind of phthalic ester and the quantitative and qualitative selection ion of internal standard compound table
For judging the accuracy of the assay method of phthalic acid ester content in certain cigarette tipping paper that embodiment 1 provides, this assay method is carried out the recovery of standard addition test.The cigarette tipping paper sample that the embodiment 1 that it is 0.3g that test takes by weighing two parts of quality adopts, add respectively each phthalic ester concentration of 15 μ L take accurate liquid-transfering gun and be the hybrid standard storing solution II of 1mg/mL, namely be equivalent to add respectively the n-butyl phthalate that content is 50 μ g/g, then carry out respectively the preparation of sample solution, record the selection quasi-molecular ions Area Ratio of n-butyl phthalate and interior mark Ergol with GC-MS, the substitution typical curve, the n-butyl phthalate content of trying to achieve in sample this moment is respectively 98.1 μ g/g, the recovery of standard addition that is n-butyl phthalate is 97.6%, illustrates that the assay method of phthalic acid ester content in certain cigarette tipping paper that embodiment 1 provides is accurately.
The assay method of phthalic acid ester content in certain khaki cigarette tipping paper adopts internal standard method, and experimental procedure is seen embodiment 1.
The content that determines diisobutyl phthalate in certain khaki cigarette tipping paper, n-butyl phthalate, the own ester of phthalic acid two (2-ethyl) is respectively 20.4mg/kg, 15.8mg/kg and 34.8mg/kg, does not detect other phthalic ester.
Embodiment 3
The assay method of phthalic acid ester content in certain cigarette tipping paper adopts internal standard method, and experimental procedure is seen embodiment 1.
The content that determines diallyl phthalate in this cigarette tipping paper (DAP) is 36.4mg/kg, does not detect other phthalic ester.
Embodiment 4
The assay method of phthalic acid ester content in certain cigarette tipping paper adopts internal standard method, and experimental procedure is seen embodiment 1.
The content that determines diisononyl phthalate in this cigarette tipping paper (DINP) is 69.7mg/kg, does not detect other phthalic ester.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although with reference to above-described embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (4)
1. the assay method of phthalic acid ester content in the cigarette tipping paper is characterized in that: may further comprise the steps:
(1) preparation inner mark solution
Take by weighing the internal standard compound Ergol, being mixed with concentration is the Ergol ethanolic solution of 20mg/mL;
(2) preparation sample solution
Cut the cigarette tipping paper sample, place 50mL tool plug triangular flask, in described 50mL tool plug triangular flask, accurately add 20mL ethanol, and the inner mark solution of 50 μ L; Afterwards ultrasonic extraction 30 minutes, after being cooled to room temperature, get the 1mL extract and put into 25mL tool plug triangular flask, the normal hexane that adds 1mL water and 5mL in the described 25mL tool plug triangular flask, described 25mL tool plug triangular flask is placed on the oscillator, with the speed oscillation of 200rpm 10 minutes, leave standstill, get supernatant liquor as sample solution, to be measured;
(3) preparation hybrid standard working solution
Take by weighing 18 kinds of phthalic ester standard items, be mixed with the hybrid standard working solution with seven grades of concentration gradients;
(4) GC-MS analyzing and testing
Adopt GC-MS respectively described hybrid standard working solution and sample solution to be carried out analyzing and testing, then carry out the quantitative test of phthalic ester with internal standard method, calculate the content of 18 kinds of phthalic esters.
2. the assay method of phthalic acid ester content in a kind of cigarette tipping paper as claimed in claim 1, it is characterized in that: the described 18 kinds of phthalic esters of step (3) refer to repefral (DMP), diethyl phthalate (DEP), diallyl phthalate (DAP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), phthalic acid two (2-methoxyl) ethyl ester (DMEP), phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate, di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP).
3. the assay method of phthalic acid ester content in a kind of cigarette tipping paper as claimed in claim 1 is characterized in that: the concentration of the hybrid standard working solution of step (3) preparation is: 0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL, 50 μ g/mL.
4. the assay method of phthalic acid ester content in a kind of cigarette tipping paper as claimed in claim 1, it is characterized in that: the analytical conditions for gas chromatography of step (4) is: chromatographic column: the HP-5ms Fused-silica capillary column, column length 30m, internal diameter 0.25mm, thickness 0.25 m; Injector temperature: 280 ℃, sample size: 1 L, use shunt mode, split ratio is 10:1; Temperature programme: 60 ℃ of initial temperatures, kept 1 minute, the heating rate with 20 ℃/min rises to 220 ℃ again, and then the heating rate with 10 ℃/min rises to 280 ℃, keeps 15 minutes; Carrier gas is helium, constant speed 1.0mL/min;
The mass spectrophotometry condition is: the ionization mode: electron bombardment ionization source, ionizing energy: 70eV; Transmission line temperature: 280 ℃; Ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Mensuration mode: select the scanning of ion surveillance style; Solvent delay: 6 minutes.
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| CN107655991A (en) * | 2017-09-21 | 2018-02-02 | 国家烟草质量监督检验中心 | The assay method of 6 kinds of phthalic acid esters in soil |
| CN108318463A (en) * | 2018-01-09 | 2018-07-24 | 上海烟草集团有限责任公司 | A kind of fluorescence spectrum rapid assay methods for phthalate substance in paper wrapper |
| CN108362787A (en) * | 2018-01-16 | 2018-08-03 | 国家烟草质量监督检验中心 | The assay method of harmful components in a kind of processing method of Cigarette paper sample, Cigarette paper |
| CN108680691A (en) * | 2018-05-15 | 2018-10-19 | 国家烟草质量监督检验中心 | The assay method of phthalic acid ester in essence spice for cigarette |
| CN109521134A (en) * | 2018-11-24 | 2019-03-26 | 上海化工研究院有限公司 | The deuterium-labeled own ester standard substance of phthalic acid two (2- ethyl) measures and application |
| CN113567532A (en) * | 2020-04-09 | 2021-10-29 | 湖南中烟工业有限责任公司 | Method for rapidly detecting phthalate ester components in cigarette paper |
-
2012
- 2012-10-17 CN CN2012103957580A patent/CN102998381A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 刘泽春等: "异丙醇萃取-气相色谱法同时测定烟用接装纸和包装纸中邻苯二甲酸酯类化合物", 《分析仪器》 * |
| 唐纲岭等: "烟用接装纸、内衬纸和卷烟条与盒包装纸中18种邻苯二甲酸酯的测定", 《烟草科技》 * |
| 张洪非等: "卷烟滤嘴中邻苯二甲酸酯的GC/MS测定", 《烟草科技》 * |
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| CN103852535A (en) * | 2014-03-26 | 2014-06-11 | 昆山洛丹伦生物科技有限公司 | Detecting method for phthalate acid in plastic component of electronic element |
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| CN104833734A (en) * | 2015-03-30 | 2015-08-12 | 上海安谱实验科技股份有限公司 | Method for detection of transfer volume of phthalic acid ester matters in food package material |
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| CN107389811A (en) * | 2017-07-05 | 2017-11-24 | 江苏中烟工业有限责任公司 | The assay method of diisopropyl naphthalene in cigarette tipping paper |
| CN107655991A (en) * | 2017-09-21 | 2018-02-02 | 国家烟草质量监督检验中心 | The assay method of 6 kinds of phthalic acid esters in soil |
| CN108318463A (en) * | 2018-01-09 | 2018-07-24 | 上海烟草集团有限责任公司 | A kind of fluorescence spectrum rapid assay methods for phthalate substance in paper wrapper |
| CN108362787A (en) * | 2018-01-16 | 2018-08-03 | 国家烟草质量监督检验中心 | The assay method of harmful components in a kind of processing method of Cigarette paper sample, Cigarette paper |
| CN108680691A (en) * | 2018-05-15 | 2018-10-19 | 国家烟草质量监督检验中心 | The assay method of phthalic acid ester in essence spice for cigarette |
| CN108680691B (en) * | 2018-05-15 | 2020-06-19 | 国家烟草质量监督检验中心 | Method for determining phthalate in tobacco flavor and fragrance |
| CN109521134A (en) * | 2018-11-24 | 2019-03-26 | 上海化工研究院有限公司 | The deuterium-labeled own ester standard substance of phthalic acid two (2- ethyl) measures and application |
| CN113567532A (en) * | 2020-04-09 | 2021-10-29 | 湖南中烟工业有限责任公司 | Method for rapidly detecting phthalate ester components in cigarette paper |
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